Process of making acetates.



' H. 0. GHUTE. PROCESS OF MAKING AGETATBS. APPLICATION FILED MA1L31, 190s.

Patented Nov. 16, 1909.

ISM

nvento-c Hm xv/(4% a M'-&

attorney HARRY o. CHUTE, or CLEVELAND, OHIO.

Specification of Letters Patent.

Application filed March 31, 1906. Serial No. 309,114.

imoonss or MAKING AGETATES.

Patented Nov. 16, 1909.

To all whom it may concern:

Be it known that I, HARRY OJ CHUTE, a citizen of the United States, residing in Cleveland, county of Cuyahoga, and State of Ohio, have invented certain new and useful Improvements in Processes of Making Acetates; and I hereby declare the followingto be a full, clear, and exact description of the same, such as will enable others skilled in the art to which it appertains to practice and use the same.

This invention relates to the manufacture of acetates, and consists in a method of making acetates of relatively high purity from crude pyroligneous acid by certain distillatory and other steps; all as more fully hereinafter set forth, matters of novelty being particularly pointed out'in the appended claims.

Pyroligneous acid is the aqueous portion of the distillate from the destructive distillation of wood, separated mechanically as far as possible from insoluble bodies, as tar, etc. It is a dark clear wine-colored liquid with a rank odor and unpleasant taste, consisting of a solution in water of acetic acid, methyl alcohol, acetone, etc., and contaminatedby tar, oily bodies, aldehydes, amins,

.higher ketones, etc., held in. solution and suspension by the solvent action of the acid and the spirituous bodies. It has long been a problem in the art to prepare reasonably pure acetic acid and acetates from this liquid without expensive manipulation, and it is the object of the present invention to provide a method for this purpose. Pyroligneous acid is practically useless as such owing to its unpleasant characteristics, and though it may be freed from part'of its im- 40 purities, such as tar, by distillation, certain other impurities are volatile in acid solution, and on addition of alkali these contaminate the acetate produced from distilled acid. In the manufacture off acetates of the higher grades, of which the calcium salt of at least 82 per cent. purity is the most com mon being known in the trade. as gray acetate or as graukalk it is. customary to feed the amide pyroligneous acid continuously 60 into a copper pot still and distil off everything volatile and occasionally draw ofi the accumulated tar in the bottom of the still. The weak watery distillate is neutralized with lime and evaporated to dryness. This distillation leaves most of the tarry bodies behind but carries forward to mix withthe acid all the impurities volatile with steam or from acid solution. On neutralization of this distillate, it gives gray acetate which rarely contains more than 82 per cent.

pf real acetate, in the case of the lime salt. These impurities are of two classes, the first of which are of an oily nature'and insoluble in the first runnings of distillate while the other impurities are unstable bodies, such as aldehydes and higher ketones, which are soluble in water and wood alcohol but form condensation products with excess of alkalies. These volatile impurities while mostly boiling at temperatures greater than that of water, nevertheless in these processes distil with the acid and wood spirit, obe ing in this respect the laws of mlxed flui s. In the stated processes of the older art, the distillation has been of the whole acid fluid, or of the neutralized fluid. This I have found to be irrational, and my invention consists partlyin a regulated distillation-of the acid whereby these volatile im urities may be removed in a concentrate form. While as stated, they are volatile with the acid solution as a whole, I find that they are particularly so with the concentrated vapors of the spirituous constituents, the alcohol and acetone and their homologues; with the bodies which together form wood alcohol. By conducting the heating of the pyroli neous acid in such manner that substantia y all the wood spirit is removed in concen trated form with as little of the water and'90 of the acid as possible, I find that the great bulk of these volatile 1m urities go into the distillate. In other wor s, by fractionating out the wood alcohol as concentrated a form as possible in this st distillation I remove with it these volatile impurities, leaving behind a pyroligneous acid of much purerv nature.

Though the oily impurities go over with the ,alcohol, as stated, in methodical" work they do not injure it as in certain concentrations they are practically insoluble; causing the alcohol to appear mi ky and on standin forming droplets in the wood spirit, an they can readil be separated by settling. Th s process 0 making pure wood spirit In the process forming the present preferred embodiment of my invention, I subject the crude pyroligneous acid to treatment in any return-flow rectifying still to obtain a wood spirit as concentrated and as free from water and acid as possible, simultaneously of course obtaining an unconcentrated purified acid which is as nearly as dilute as was the original acid. The residuum is a purified pyroligneous acid, now containing only the tar and non-volatile impurities, and it may be converted into a brown acetate richer in real acetate than an now on the market. \Vhen further puri cation is desired, I directly distil the whole mass of residual fluid, thereby obtaining a clear and transparent acid free of tar and non-volatile impurities, as well as free of the volatile impurities removed in the fractionation. This acid is suitable for use as such for many purposes, or it may be neutralized to obtam a pure gray acetate. When this urified acetate is sought, however, I pre erabl combine its manufacture with the dist' lation, thereby economizing in heat and labor. For

this pur ose I conduct the vapors of the boiling liquid, previously purified from volatile impurities as described, through or over a base, maintained at a temperature above the boiling point of water, but below that of the saturated solution of the articular acetate formed. The base, then a sorbs the acid from the vapors, while permitting steam to go on and the acetate formed passes 011" in the form of a saturated solution which may be handled with much less expense than if I the whole volume of vapors had been condensed, the base added and then the water evaporated .ofl". Having the water in the form of steam in the distillation, it is obvious that it is uneconomical to condense it and then revaporate. L

The neutralization is preferably performed in a methodical manner, the acid vapors being introduced into a conduit or receptacle at the one end while alkali is introduced at the other. The excess of steam.

is allowed to escape uncondensed from the end of the conduit at which the alkali is introduced, while concentrated acetate solution is removed from the end at which the acid va ors are introduced.

The Ease in this process may be any one In the accompanying illustration I show,

more or less diagrammatically, one form of apparatus of the many adapted to perform my process.

In this illustration1 is an acid pump delivering pyroligneous acid through lpe 2 to a pre-heater 3, containing a nest 0 tubes 4, through which it flows. Leaving the preheater through pipe 5, the acid enters the upper ptrtion of distilling column 7 provided with perforatedshelves 8, cups 9 and downtake tubes 10, and travels'downward in a well-understood Way until it entersthe lower chamber 11. This chamber is provided with an exit pipe 12, valved at 13 and provided with a float 14 regulating the valve.

Through this pipe it flows to equalizing chamber 15, provided with a vent-pipe 16..

Returning tothe description of the still,

this is provided with man-holes 35 throu h which the cups and downtake tubes can, e

cleaned or removed, if made removable, this,

structure being necessary for the reason that tar is liable to accumulate in these elements.

The wood alcohol vapors formed in this still I leave through pipe 36, pass around the tubes of the pre-heater, where a portion of the water is condensed out under the influence of the infiowing cold, or relatively cold, acid, and is returnedto the still through the goose-neck 37 for retreatment, since it of course carries more or less of the alcohol. The uncondensed vapors leave the pre heater through pipe 38, are condensed in the condenser 39 and exit through pipe 40.

The heat necessary for running the still is furnished in a separate boiler 41, heated by steampassing around a nest of internal tubes (not shown). The necessary circulation of this heater instead of being furnished by a large central tube, as in ordinary evaporators, is furnished by external, air-cooled tubes 42. Tar-free liquor is drawn off from near the surface of the liquid in the bottom chamber of the still by'means of a pipe 43, boiled in the heater and the vaporsreturned to said ha-mber by means of pipe 44.

In order to follow the pro ess of the distillation in the still, I provi e it with a testing device consisting of a condenser 45 com-- oints municating with the still at various (two are shown) by means of a valve I pipe connection 46. The condensate from this passes into a 'hydrometer jar 47. The pressure in the still may be estimated by the manometric device 48 connectedwith the,

steam space of the bottom chamber by means of pipe 49. Pressure and temperature, of course, correspond. The pressure in the still is sufiicient to force liqmd into the equalizing (15).

In the operation of the column still (7), the liquid drawn off from the bottom chamber, 11, of the column is boiled in boiler 41, and the vapors, which are free of spirit, return through pipe 4:4: into said chamber and thence upward through the column against the descending acid, distilling the spirit and the low boiling bodies therefrom in the wellunderstood way. The inflowing liquid from 5 is delivered at a point in the column where w the average contents in spirit and acid of the liquid under treatment in the column is aboutvthe same as its own contents in those substances.

The purified pyroligneous acid delivered into tank is fed automatically through the pipe 17, regulated by the float controlled valve mechanism 18 keeping the still 19 filled to an approximately constant height.

This method of operation causes the outflowing vapors to contain acid and water 1n the same relatlve proportions as the inflowing liquid acid. The heating coils 20 distil the acid and water through the neck 21 into the saturator 22, the vapors passing through the perforated plates 23 and coming into contact with alkali which neutralizes the acid, and the water vapor passes freely into the atmosphere at the top of the-saturator which is left open for that purpose. The alkali, as lump lime, for instance, isplaced on the top plate of the saturator and kept constantly replenished as it dissolves under the action of the passing steam and acid. Quicklime hydrates and breaks downinto milk of lime which flows downward through the saturator in the opposite direction to the upward flow of acid vapors, reaching the base of the saturator as a saturated so-' lution of acetate. The solution is held on the perforations by the pressure of steam passing through, but when the li uid on the plates reaches the level of the own pipes 25, the liquid passes down and is trapped in the cups 26, overflowing on the plate. It so passes to the bottom chamber 27 and escapes constantly by the pipe'28, regulated by the valve 29 and float 30, the rising of the liquor in the bottomchamber raising thefloat and opening the valve 29. The non-volatile impurities are drawn off from the still intermittently by the tar gate 31. r

By using lime as the neutralizing alkali in the hot neutralizing method described and replenishing the supply with quicklime-the .heat of slaking and neutralization sufices to .keep the temperature of the neutralizing apparatus at the re uired point. Using other alkalies, ordinari y a supply of heat from some extraneous source, may be required. With quicklime placed upon the upper shelf 23 of the neutralizer shown, sufficient water will be condensed from the flow of steamto form milk of lime which passes downward through the various shelves becoming more and more neutralized as it progresses until finally a concentrated solution of neutral acetate is drawn off through 28.

v To recapitulate: My process in its present preferred form consists in purifying pyro ligneous acid by distilling off volatile, al-

kali-sensitive impurities,impurities compr1smg aldehydes, ketones, Olly bodiesand creosotes; in distilling off from the purified.-

'iyroligneous acid the acetic acid with the water; in passing these vapors through a counter current of alkali in solution or suspension at atemperature at which water vapors will not condense, allowing them to escape into the air while neutralizing the acid vapors with the alkali, and in with drawing the concentrated acetate so produced.

V hat I claim is:

1. In the manufacture of acetates, the process which consists in fractionating out concentrated wood alcohol and accompanying volatile impurities from pyroligneous acid, distilling the residual acid and saturating the acid inthe vapors with a base at a temperature above the boiling point water.

2. In the manufacture of acetates, the process which consists in fractionating out concentrated Wood spirit and accompanyin volatlle impurities from pyroligneous ac1 distilling theresidual acid and saturating the acid in the vapors with lime at a tem-T perature above the'boiling polnt of water. 3. In the -manufacture of acetates, the

process which comprises fractionating away concentrated Wood spirit and accompanying impurities from pyroligneous acid to produce a purified substantially unconcentrated acid, distilling such acid as a whole and passing the vapors to exit through a conduit maintained above the boiling point of water,alkali being fed into the vapor exit end of such conduit and acetate solution removed from the vapor inlet end.

4. In the manufacture of acetates, the

process which consists in fractionating concentrated wood alcohol and accompanying impurities from pyroligneous acid, dlstilling the purified acid, and neutralizing the acid in the vapors by passing said vapors past a plirities from pyrolig'neous acid continumbov e the boiling point of water, whereby a ously supplying thepurified acid to a still gconc'entrated solutlon of acetate is formed. 10 in the same amount as acid va ors distil I 'In testimony whereof, I affix my Sign! therefrom, whereby the richness o inflowing itnre in the presence of two witnesses.

5 liquid and outfiow'ing' vapors is rendered a HARRY O. CHUTE,'

substantially the same, and passing such out- \Vitnesses: flowing acid vapors past a bodyofalkali BLANGHE L. CHADWELL,

maintained at a temperature" somewhat 4 K. P. MOELROY. 

